DE69829373T2 - Polymerization - Google Patents

Polymerization

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Publication number
DE69829373T2
DE69829373T2 DE1998629373 DE69829373T DE69829373T2 DE 69829373 T2 DE69829373 T2 DE 69829373T2 DE 1998629373 DE1998629373 DE 1998629373 DE 69829373 T DE69829373 T DE 69829373T DE 69829373 T2 DE69829373 T2 DE 69829373T2
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Germany
Prior art keywords
liquid
reactor
bed
stream
fluidized bed
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Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
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DE1998629373
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German (de)
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DE69829373D1 (en
Inventor
Dominique Erick DAIRE
Jean-Pierre Isnard
Viviane Claudine LALANNE-MAGNE
Patrice Bruno SOULIER
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Petroineos Europe Ltd
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BP Chemicals Ltd
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Publication date
Priority to EP97430017 priority Critical
Priority to EP97430017 priority
Application filed by BP Chemicals Ltd filed Critical BP Chemicals Ltd
Priority to PCT/GB1998/001639 priority patent/WO1999000430A1/en
Publication of DE69829373D1 publication Critical patent/DE69829373D1/en
Application granted granted Critical
Publication of DE69829373T2 publication Critical patent/DE69829373T2/en
Anticipated expiration legal-status Critical
Application status is Expired - Lifetime legal-status Critical

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Classifications

    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F10/00Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10STECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S526/00Synthetic resins or natural rubbers -- part of the class 520 series
    • Y10S526/901Monomer polymerized in vapor state in presence of transition metal containing catalyst

Description

  • The The present invention relates to a continuous process for the Gas phase polymerization of olefins in a fluidized bed reactor with improved levels of productivity without pollution. The present The invention also relates to a starting method of a continuous one Procedure for the gas phase polymerization of olefins in a fluidized bed reactor with improved levels of productivity without pollution. The present The invention further relates to a method for handling the Events during a continuous process for gas phase polymerization of olefins in a fluidized bed reactor with improved levels of productivity without pollution.
  • method for the homopolymerization and copolymerization of olefins in the Gas phase are well known in the art. Such procedures can for example through the introduction of the gaseous Monomers in a stirred and / or fluidized bed, the polyolefin and a catalyst for the polymerization, are carried out.
  • at fluidized bed polymerization of olefins, the polymerization is in a fluidized bed reactor carried out, wherein a bed of polymer particles by means of an ascending gas stream, comprising the gaseous Reaction monomer is kept in a fluidized state. The start of such polymerization generally begins Bed of polymer particles, similar a polymer that desirably to be produced. While the course of the polymerization becomes fresh polymer through the produced catalytic polymerization of the monomer, and the polymer product is subtracted to the bed at a more or less constant To keep volume. An industrially preferred method begins Fluidizing grid to distribute the fluidising gas in the bed, as a carrier for the Bed acts when the supply of gas is disconnected. The manufactured Polymer is generally discharged from the reactor by means of a discharge channel, the arranged in the lower part of the reactor near the fluidizing grid is deducted. The fluid bed includes a Bed of growing polymer particles, polymer product particles and Catalyst particles. This bed is made by the continuous Upward flow of one Fluidizing gas, the recycle gas from the upper end of the reactor, together with auxiliary feed, from Bottom of the reactor kept in a fluidized state. The fluidizing gas enters the bottom of the reactor and passes through, preferably through a fluidizing grid, into the fluidized bed.
  • The Polymerization of olefins is an exothermic reaction and it is therefore necessary means for cooling of the bed to provide the heat from the polymerization to remove. In the absence of such cooling would the temperature of the bed increase until, for example, the catalyst would become inactive or the bed would start to melt. In fluidized bed polymerization Of olefins is a preferred method for the removal of heat the polymerization, the supply of a gas, the fluidizing gas, the at a temperature lower than the desired polymerization temperature is present, to the polymerization reactor, passing the gas through the fluidized bed, for the heat to conduct away from the polymerization, removing the gas from the Reactor and cooling, by passing it through an external heat exchanger, and returning to the bed. The temperature of the recirculation gas can in the heat exchanger be set so that the fluidized bed at the desired Polymerization temperature is maintained. In this procedure the Polymerization of alpha-olefins generally involves the recycle gas monomeric olefin, optionally together with, for example, one inert diluent gas like Nitrogen and / or a gaseous Chain transfer agents like hydrogen. Therefore, the recycle gas serves the monomer to feed the bed, Fluidize the bed and put the bed where you want it Keep temperature. Monomers produced by the polymerization reaction are consumed normally by the addition of additional Gas to the recycle gas stream replaced.
  • It is well known that the rate of production (ie, the space-time yield relative to the weight of the polymer produced per unit volume of reactor space per unit time) in commercial gas moving bed reactors of the above type is indicated by the maximum rate the heat can be removed from the reactor is limited. The rate of heat removal can be increased, for example, by increasing the velocity of the recycle gas and / or reducing the temperature of the recycle gas and / or changing the heat capacity of the recycle gas. However, there is a limit to the speed of the recycle gas that can be used in commercial practice. Below this limit, the bed may become unstable or even leak out of the reactor into the gas stream, resulting in blockage of the recycle line and damage to the recycle gas compressor or blower. There is also a limitation on the extent to which the recycle gas can be cooled in practice. This is primarily due to economic considerations and in practice usually by the temperature of the industrial Cooling water, which is available on site, determined. The cool storage can be used as needed, but this adds to the cost of production. Therefore, the use of cooled recycle gas as the sole means of removing the heat of polymerization from the fluidized bed polymerization of olefins has the disadvantage of limiting the maximum available production rates.
  • Of the State of the art suggests a variety of methods for increasing the heat removal capacity of the recycle stream in front.
  • EP 89691 refers to a method for increasing the space-time yield in continuous fluidized bed processes for the polymerization of fluid monomers, the method comprising cooling some or all of the unreacted fluids to form a two-phase mixture of gas and entrained liquid below the dew point , and the reintroduction of the two-phase mixture into the reactor. The description of EP 89691 indicates that a primary limitation on the extent to which the recycle gas stream can be cooled below the dew point is provided that the gas to liquid ratio be maintained at a level sufficient to maintain the liquid phase of the two phase fluid mixture in a entrained or suspended state until the liquid has evaporated, and further indicates that the amount of liquid in the gaseous phase should not exceed about 20% by weight, and preferably should not exceed about 10% by weight, always provided that the rate of the two-phase recycle stream is high enough to keep the liquid phase in suspension in the gas and carry the fluidized bed in the reactor. EP 89691 further discloses that it is possible to form a two-phase fluid flow in the reactor at the time of injection by separate injection of gas and liquid under conditions which will produce a two-phase flow, but there is a small advantage in operating in this way due to the additional and unnecessary burden and the cost of separating the gas and liquid phases after cooling.
  • EP 173261 refers to a particular means of introducing a recycle stream into fluidized bed reactors and, more particularly, to a recycle stream introduction means comprising a two phase mixture of gas and entrained liquid, as in US Pat EP 89691 (above).
  • WHERE 94/25495 describes a fluidized bed polymerization process, comprising the conduit of a gaseous Stream comprising monomer, through a fluidized bed reactor in the presence of a catalyst under reactive conditions, to make a polymeric product, and a stream that is not comprises reacted monomer gases, Compress and cool of the stream, mixing the stream with feed components and Return of a Gas and liquid phase to the reactor, a method for determining stable working conditions, that: (a) observation of changes the fluidized bulk density in the reactor with changes the composition of the Fluidisiermediums related; and (b) increase the cooling capacity of the recycle stream through the change of the composition without exceeding the level at which a Reducing the fluidized bulk density or a parameter the one for this is indicative, becomes irreversible.
  • US 5,436,304 relates to a process for the polymerization of alpha olefin (s) in a fluidized bed gas phase reactor and a fluidising medium, wherein the fluidising medium serves to control the cooling capacity of the reactor, and wherein the bulk density function (Z) is at a value equal to or equal to greater than the calculated limit of the bulk density function.
  • WHERE 94/28032, the contents of which are hereby incorporated by reference, refers to a continuous gas moving bed process wherein the recycle gas stream cooled to a temperature will be enough to make a liquid and to form a gas. By separating the liquid from the gas and then feeding it the liquid directly into the fluidized bed at or above the point where the gaseous Electricity flowing through the fluidized bed running, has essentially reached the temperature of the gaseous stream, withdrawn from the reactor, the total amount of liquid, the back into the fluidized bed polymerization reactor for the purpose of cooling bed is introduced by evaporation of the liquid, elevated which reduces the level of cooling reinforced can be higher productivity levels to reach.
  • The separate liquid suitably in the fluidized bed by means of one or more Nozzles that are arranged to be injected. The nozzles may be either gas atomizing nozzles, in which a nebulizer gas is used to assist the injection of the fluid, or you can Be nozzles, the only liquid spray.
  • The above disclosed methods all contribute to the levels of productivity that are found in fluidized bed can be achieved, which is also one of the objectives of the present invention. However, it is known in the art that a major problem encountered in these highly productive polymerization processes is the fouling phenomenon that can occur in the reactor at any point in time.
  • The Soiling of the reactor wall is a well-known phenomenon the gas phase polymerization. While Polymerisationsfeinteilchen can stick to the reactor wall and Form agglomerates; sometimes this can be explained by the liability of catalyst and polymer particles that melt on the reactor wall result. Their presence very often induces fluidisation disorders that are irreversible Can cause problems. If For example, if these agglomerates become heavy, they can fall off the wall and block the fluidizing grid and / or the polymer exhaust system. The accumulation of fine particles and / or agglomerates on the reactor wall is therefore called the pollution phenomenon.
  • It There are many revelations in the art that relate to pollution phenomena. as well as many different explanations and theories in relation on their occurrence. The type of catalyst that is used should for to be responsible for polluting; static electricity is as well as a reason for the fouling has been stated; Working conditions are the same as for the occurrence of pollution has been considered important; actually has a professional develops as many different possible explanations and solutions as far as the occurrence of soiling is concerned. It would be a great advancement in technology when the pollution phenomena either remarkably reduced or eliminated, which always the explanation for their Occurrence may be.
  • It is now surprising found out that where pollution problems occur, these through use the method according to the present invention Remarkably reduced or even eliminated can.
  • It Now, a method has been found that on a continuous introduction of condensed liquid is based in the reactor, which has no adverse effect on the composition of the fluidized bed that does not affect the fluidization conditions in the reactor and that potential pollution phenomena remarkably reduced or even eliminated in the reactor.
  • Thus, according to the present invention, there is provided a continuous fluidized bed process for the polymerization of an olefin monomer selected from (a) ethylene, (b) propylene, (c) mixtures of ethylene and propylene and (d) one or more other alpha-olefins, which are mixed with (a), (b) or (e) in a fluidized bed reactor by continuously recycling a gaseous stream comprising at least one of ethylene and / or propylene through the fluidized bed in the reactor in the presence of a reactive polymerization catalyst Conditions provided, characterized in that the recirculated gaseous stream withdrawn from the reactor, in two streams (A and B) is divided and that
    • (a) a first stream (A) which has been cooled to a liquid condensing temperature, then reintroduced directly into the fluidized bed in the reactor so that the condensed liquid is continuously fed to the bed at any one time minimum speed of 101 liquid per cubic meter of fluid bed material per hour, and
    • (B) a second stream (B), which bypasses the above cooling / condensation step, is passed through a heat exchanger and then reintroduced into the reactor.
  • According to the present Invention, it is now possible early one Part of the recycle gas stream to condense and the condensed liquid directly into the fluidized bed at very low production rates, or preferred before production starts to introduce. The control of the polymerization reaction is thereby during the Starts the process much easier in a stationary state kept and the amount of liquid, into the fluidized bed entry is much easier without disturbing the Fluidisiermerkmale of the procedure. One of the most interesting advantages according to the present Invention are found, the positive influence of the present method to the consecutive potential Polymerization problems, with which one is familiar with the very productive Polymerization method, as demonstrated in the accompanying examples.
  • In particular, it has now been found that the continuous introduction of the condensed liquid into the bed at a minimum rate of 10 liters of liquid per m 3 of fluidised bed during the entire process, that is, from the early beginning and at any subsequent time, a remarkable reduction or even the Elimination of all of the above-mentioned polymerization contamination problems. It has also been found that the presence of the second stream (B) and its passage through a heat exchanger according to the present invention is mandatory. In fact, working with the second stream (B) of the present invention enables the process to satisfy both heat and mass equilibrium.
  • Prefers becomes the condensed liquid directly into the fluidized bed above the upper limit of the temperature gradient between the incoming Fluidizing gas (the gaseous Current feed to the reactor) and the rest of the bed.
  • According to the present Invention may be the amount of liquid, the directly into the fluidized bed is injected, by the regulation of the part of the gaseous stream, the cooled is controlled to form the biphasic mixture.
  • By the use of the method according to the present invention the reaction control is kept in a steady state. Also the start of the injection of liquid can be carried out with a small investment run and the conversion of conventional Procedure can be carried out at low capacities if the fluidized bed not very active. According to one preferred embodiment The present invention begins the cooling / condensation step and the introduction the condensed liquid in the reactor bed before the introduction of the active catalyst in the reactor and / or before the polymerization takes place; under these starting conditions becomes the second stream (B) sufficiently through the heat exchanger heated to the growing cooling, the from the injection of fluid results in balancing, whereby the heat balance in the process is maintained.
  • The respective parts of the streams (A) and (B), wherein (A) the cooling / condensation step and (B) passes through the heat exchanger, hang from the stage in which the procedure is located.
  • Of the gaseous Recycle stream, which is withdrawn from the reactor generally comprises unreacted gaseous Monomer (s) and optionally inert hydrocarbon (s), inert Gases such as nitrogen, reaction activator (s) or moderator (s) such as hydrogen, as well as entrained catalyst and / or Polymer particles (hereinafter referred to as fine particles). The main part This fine particle can advantageously from the gaseous recycle stream be removed by means of a cyclone.
  • Of the gaseous Recycle stream, which is fed into the reactor additionally comprises sufficient additional monomers, to replace the monomers that were polymerized in the reactor.
  • The process according to the present invention is suitable for the preparation of polyolefins in the gas phase by the polymerization of one or more olefins, at least one of which is ethylene or propylene. Preferred alpha-olefins for use in the process of the present invention are those having from 3 to 8 carbon atoms. Small amounts of alpha olefins of more than 8 carbons, for example 9 to 18 carbons, can be used as needed. Therefore, it is possible to prepare homopolymers of ethylene or propylene or copolymers of ethylene or propylene with one or more C 3 -C 8 alpha-olefins. The preferred alpha olefins are but-1-ene, pent-1-ene, hex-1-ene, 4-methylpent-1-ene and oct-1-ene. Examples of higher olefins that can be copolymerized with the primary ethylene or propylene monomer or as a partial replacement for the C 3 -C 8 alpha-olefin comonomer are dec-1-ene and ethylidenenorbornene.
  • If the method for the copolymerization of ethylene or propylene with alpha olefins is used, is ethylene or propylene as the Main component of the monomers, and is preferably in an amount of at least 65% of the total monomer / comonomer.
  • The Method according to the present invention This invention can be used to produce a wide range of polymer products used, for example, linear low density polyethylene (LLDPE) based on copolymers of ethylene with but-1-ene, 4-methylpent-1-ene or hex-1-ene and high density polyethylene (HDPE), for example Homopolyethylene or copolymers of ethylene with a small proportion higher alpha olefin, for example, but-1-ene, pent-1-ene, hex-1-ene or 4-methylpent-1-ene, can be.
  • The liquid that condenses from the gaseous recycle stream may be or may be a condensable monomer, for example, but-1-ene, hex-1-ene, oct-1-ene, which is used as a comonomer for the production of LLDPE an inert condensable liquid, for example inert hydrocarbon (s) such as C 4 -C 8 alkane (s) or cycloalkane (s), in particular butane, pentane or hexane.
  • It is important that the liquid in the bed under the polymerization conditions that are used evaporates, so that the desired cooling effect is obtained and considerable Accumulation of liquid to avoid in the bed. Suitably, at least 95, preferably at least 98% by weight, and most preferably substantially the entire liquid, which is fed into the bed, in it. In the case of liquid comonomers polymerize some of the copolymers in the bed and such Polymerization may be from the liquid and the gas phase take place. The associated olefin monomer can be found in be easily tolerated the bed, provided that the quantities do not adversely affect the fluidising characteristics of the bed.
  • The Procedure is especially for the polymerization of olefins at an absolute pressure between 0.5 and 6 MPa and at a temperature between 30 ° C and 130 ° C suitable. For example, the temperature for LLDPE production is appropriate in the range of 70 to 90 ° C and for HDPE is the temperature typically 80 to 105 ° C, depending on the activity of the used Catalyst.
  • The Polymerization reaction can be carried out in the presence of a catalyst system be carried out by the Ziegler-Natta type, that of a solid catalyst, which is essentially a compound from a transition metal comprises and a cocatalyst which is an organic compound a metal (i.e. an organometallic compound, for example an alkylaluminum compound) consists. High-active catalyst systems have been around for many years known and can size Generate quantities of polymer in a relatively short time, causing the Need for removal of catalyst residues from the polymer was eliminated. These highly active catalyst systems generally include one solid catalyst consisting essentially of atoms of transition metals, Made of magnesium and halogen. It is also possible one to use highly active catalyst, consisting essentially of a Chromium oxide, activated by a heat treatment and connected with a granular Carrier, on a heat resistant Oxide based, exists. The method is also for use with metallocene catalysts either supported or unsupported and Ziegler catalysts supported on silica.
  • Of the Catalyst may suitably be in the form of a prepolymer powder be used previously during a Präpolymerisationsstadiums with the aid of a catalyst as described above. The prepolymerization can be carried out by any suitable method, for example, by polymerization in a liquid hydrocarbon diluent or in the gas phase using a discontinuous Process, a semi-continuous process or a continuous one Process.
  • Of the first stream (A) is cooled to a temperature at which liquid in the gaseous Recycle stream is condensed. This is preferably done by means of a heat exchanger or exchangers. Suitable heat exchangers are well known in the art.
  • Of the second stream (B) is running through one or more heat exchangers. The / the heat exchanger can the gaseous Either cool electricity or warm up, dependent on of the process stage.
  • According to one another preferred embodiment of the present invention, the condensed liquid, generated in the first stream (A) by the cooling / condensation step was, then from the gaseous Current is separated before it is introduced into the bed.
  • In a still other embodiment In the present invention, the second stream (B) is replaced by a heat exchangers cooled to a temperature at the liquid condensed, the condensed liquid separated from the stream before it is inserted into the bed.
  • suitable Means for separating the liquid For example, there are cyclone separators, large vessels that control the speed reduce the gas flow to bring about the separation (knock-out Drums), gas-liquid separator of the demister-type and liquid scrubber, to Example venturi scrubber. Such separators are well known in the art.
  • The Use of gas-liquid separators The demister type is in the process of the present invention particularly suitable.
  • One Another advantage of using demister-type separators is that the pressure drop in the separator may be lower than in other types of separators, reducing the efficiency of the Overall procedure increased can be.
  • One particularly suitable demister separator for use in the process the present invention is a conventionally available vertical gas separator, known as a "Peerless" (type DPV P8X) Coalescence of liquid droplets on a baffle arrangement is used on separators for the separation of the liquid out of the gas. A big liquid reservoir will be on the bottom of the separator to collect the liquid wherein the condensable liquid is charged before the gaseous Recycle stream cooled to a temperature will, at the liquid condensed out. The liquid reservoir allows it's the liquid store control of the introduction of the liquid from the separator into the fluidized bed can be provided. This type of separator is very efficient and gives a 100% separation of the condensed liquid from the gas stream. The separated liquid washes any fine particles from the baffle arrangement, causing pollution of the baffles is avoided.
  • The condensed liquid, either directly from the cooling / condensation step or was generated from the separator (preferred embodiment), is then preferred in the fluidized bed over the upper limit of the temperature gradient between the entrance of the Fluidizing gas and the rest of the bed introduced. The introduction of condensed liquid can be at a variety of points in this area of the fluidized bed take place and these can lie in different heights in this area. The point or the points of introduction the liquid are arranged so that the local concentration of liquid the Fluidization of the bed or the quality of the product is not detrimental impaired and it allows the liquid can be quickly distributed from any point and evaporated in the bed, to the heat of Remove polymerization from the exothermic reaction. To this Way, the amount of liquid, for cooling purposes introduced will, much closer correspond to the maximum charge that can be tolerated without that the Fluidisiermerkmale the bed are disturbed, and therefore the possibility offer, increased Levels of reactor productivity to reach.
  • The liquid can be placed in the fluidized bed as needed at different heights be introduced into the bed. Such a technique can provide improved control over the comonomer incorporation facilitate. A controlled dosage of the liquid in the fluidized bed provides a useful one additional control over the temperature profile of the bed and in the event that the liquid Contains comonomer, a useful one Control over the comonomer incorporation in the copolymer.
  • The liquid is preferred in the lower part of the area of the fluidized bed over the upper limit of the temperature gradient between the incoming Fluidizing gas and the rest of the bed introduced. Conventional methods for gas fluidized bed polymerization olefins are generally subject to essentially isothermal, stationary Conditions performed. Although, however, almost the entire fluidized bed is at the desired is maintained at a substantially isothermal polymerization temperature, There is usually a temperature gradient in the area of the bed immediately above the point of introduction of the chilled Gas stream is in the bed. The lower temperature limit of this Area where the temperature gradient exists is the temperature of the incoming Cooling gas flow, and the upper limit is the substantially isothermal bed temperature. In conventional Reactors of the type that employ a fluidizing grid, usually 10 to 15 m high, this temperature gradient normally exists in a layer of about 15 to 30 cm (6 to 12 inches) above the Grid.
  • Around the maximum benefit of cooling the condensed liquid It is important to achieve that Liquid injection means in the bed over the area where this temperature gradient exists, d. H. in the part of the bed, which is essentially the temperature of the gaseous Stream that leaves the reactor reached Has.
  • Of the Point or points of introduction the liquid into the fluidized bed can / can for example about 50 to 200 cm, preferably 50 to 70 cm above the fluidizing grid.
  • In In practice, the temperature profile in the fluidized bed may first during the Polymerization, for example using thermocouples, in or on the walls of the reactor are determined. The point or the Points of introduction the liquid is / are then arranged so as to ensure that the liquid entering the area of the bed at which the recirculated gas stream has substantially reached the temperature of the gaseous recycle stream, which is withdrawn from the reactor.
  • It It is important to ensure that the temperature in the fluidized bed at is maintained at a level below the sintering temperature of the polyolefin that makes up the bed.
  • The Gas from the second stream (B) and from the separator, if used, is returned to the bed, preferably in the bottom of the reactor. If a Fluidisiergitter used finds such recycling preferred in the area under the grid instead, and the grid facilitates the even distribution the gas that is supposed to fluidize the bed. The use of a Fluidisiergitters is preferred.
  • The Method of the present invention is with a gas velocity in the fluidized bed carried out, the bigger or it must be the same which is required to achieve a bubbling fluidized bed. The minimum gas velocity is generally about 6 cm / s, but the process of the present invention is preferred using a gas velocity in the range of 30 to 100, most preferred 50 to 70 cm / s performed.
  • Of the Catalyst or the prepolymer can be used as needed in the fluidized bed directly be introduced with the flow of the condensed liquid, whether separate or not. This technique can be improved Dispersion of the catalyst or prepolymer in the bed lead. By Inject the condensed liquid into the fluidized bed In this way, any catalyst that is in the liquid can There is a benefit from the localized cooling effect the liquid penetration, which surrounds each injection, draw what hot spots and consequently avoids agglomeration.
  • If required can liquid or liquid-soluble additives, for example activators, cocatalysts and the like in the Bed, along with the stream of condensed liquid, separate or not become.
  • In the case, that this Method of the present invention is used to ethylene homo or copolymers may produce additional ethylene, for example, around the ethylene that while The polymerization was consumed to replace, advantageously at every point where the recirculation stream down the cooling / condensation heat exchanger (A) running, and before its introduction in the bed (for example, under the fluidizing grid, if one such was used) introduced become. By adding the extra Ethylene at this point, the amount of liquid that can be removed from the heat exchanger (A) is returned, elevated and productivity be improved.
  • The condensed liquid can in the fluidized bed be introduced by any suitably arranged injection means. It can be used a single injection or it For example, a variety of injectables can be placed in the fluidized bed become.
  • A preferred arrangement provides a variety of injection means ready in the fluidized bed in the field of introduction the liquid are substantially equally spaced. The number of injectables, which are used is the number required to get sufficient Penetration and dispersion of the liquid with each injection to provide a good dispersion of the fluid through the bed to reach. A preferred number of injectables is four.
  • each The injectant may be mixed with the condensed liquid as needed by means of a common conduit disposed in the reactor is fed become. This can be done, for example, with a line leading to the center of the reactor leads, to be provided.
  • The Injection means are preferably arranged to be can extend substantially vertically into the fluidized bed, however be arranged so that they from the walls protrude of the reactor in a substantially horizontal direction.
  • The preferred injection means is a nozzle or a plurality of nozzles, the Include gas-induced atomizing nozzles, wherein a gas is used when injecting the liquid is helpful, or spray nozzles only for liquid.
  • suitable Gas-induced atomizing nozzles and Only liquid nozzles are in WO 94/28032 and WO 96/20780, the contents of which are hereby incorporated by reference are incorporated by reference.
  • As stated previously, the present invention requires the continuous introduction of condensed liquid into the bed at a minimum rate of 101 liquid per cubic meter of fluid bed material per hour. Preferably, the rate is greater than 40 liters of fluid per cubic meter of fluid bed material per hour. The highest rate at which liquid can be introduced into the bed depends primarily on the degree of cooling required in the bed, which in turn depends on the rate of production of the bed from. The rates of production obtainable from the commercial fluidized bed polymerization processes for the polymerization of olefins depend, inter alia, on the activity of the catalysts used and the kinetics of such catalysts.
  • It It has also been found that the present invention especially for the handling of events useful is that while a continuous Polymerisati onsverfahrens can occur. The usual Events that are referred to in a continuous polymerization process can, can for example, an interruption of the catalyst injection, a partial Poisoning of the reaction or a mechanical failure. At acquaintances usual highly productive (condensation) processes lead to these events Loss of production and at a time when working in a non-condensation mode becomes. It has been observed that the periods of the non-condensation procedure for the procedure harmful are, and systematic to subsequent pollution problems to lead. It has unexpectedly been found that the present invention, which continuously runs in condensation mode, provides a means substantially reduced by the fouling problems or can be completely eliminated.
  • In yet another aspect of the present invention, there is provided a start-up process of a continuous fluidized bed process for the polymerization of an olefin monomer selected from (a) ethylene, (b) propylene, (c) mixtures of ethylene and propylene, and (d) one or more other alpha-olefins mixed with (a), (b) or (c) in a fluidized bed reactor by continuously recycling a gaseous stream comprising at least one of ethylene and / or propylene through the fluidized bed in the reactor in the Presence of a polymerization catalyst under reactive conditions, characterized in that the recycled gaseous stream withdrawn from the reactor is divided into two streams (A and B) and
    • (a) a first stream (A) which has been cooled to a liquid condensing temperature, then reintroduced directly into the fluidized bed in the reactor so that the condensed liquid is continuously fed to the bed at any one time minimum speed of 101 liquid per cubic meter of fluid bed material per hour, and
    • (B) a second stream (B), which bypasses the above cooling / condensation step, is passed through a heat exchanger and then reintroduced into the reactor.
  • The Starting method according to the present Invention begins before the introduction of the active catalyst in the reactor and / or before the polymerization takes place. Therefore starts according to this preferred embodiment the cooling / condensation step and the introduction the condensed liquid in the reactor bed before the introduction of the active catalyst in the reactor and / or before the polymerization starts. Under these starting conditions, the second stream (B) through the heat exchanger sufficiently heated, to the growing cooling, from the injection of liquid results in balancing, whereby the heat balance in the process is maintained.
  • According to one another preferred embodiment The present invention provides the catalyst or prepolymer into the fluidized bed directly with the flow of condensed liquid, whether separate or not, introduced. The benefits associated with this technique are an improved dispersion of the catalyst at an early stage the process, which helps to create hot spots during the process Start process and therefore prevent the subsequent agglomeration.
  • In front the introduction the liquid by the use of the method of the present invention the gas-phase fluidized bed polymerization be started by loading the bed with particulate polymer particles and then the gas / liquid flow through the bed is initiated.
  • The Methods of the present invention will now be described with reference to the attached Drawings illustrated.
  • The 1 to 3 schematically show methods according to the present invention.
  • 1 illustrates a gas phase fluidized bed reactor consisting essentially of a reactor body ( 9 ), which is generally an upright cylinder with a fluidizing grid mounted on its base. The reactor body comprises a fluidized bed ( 11 ) and a speed reduction zone ( 12 ), which generally has a larger cross-section compared to the fluidized bed.
  • The gaseous reaction mixture leaving the upper part of the fluidized bed reactor forms a gaseous recycle stream and is conveyed by a conduit ( 13 ) to a cyclone ( 14 ) to separate out the majority of fines. The removed fines are suitably returned to the fluidized bed. The gaseous recirculation flow leaving the cyclone passes to a compressor ( 15 ). The gaseous recycle stream is then separated into a first stream (A) and a second stream (B).
  • Stream (A) is passed through a heat exchanger ( 16 ), where it is cooled to a temperature at which liquid condenses out, and then re-introduced directly into the fluidized bed in the reactor.
  • Stream (B) is passed through an exchanger ( 18 ) and then reintroduced into the reactor under the sieve. The gas is directed to the bed by means of the fluidizing grid, ensuring that the bed is maintained in a fluidized state.
  • A valve ( 17 ) is used to regulate the respective amounts of gaseous streams A and B.
  • The catalyst or prepolymer is added to the reactor by means of the line ( 20 ) are fed into the flow of condensed liquid.
  • The product polymer particles are removed from the reactor via line ( 21 ) away.
  • 2 Figure 1 illustrates a preferred embodiment for carrying out the method of the present invention. In this arrangement, after the cooling / condensation step in the heat exchanger ( 16 ) the resulting gas-liquid mixture to the separator ( 22 ), where the liquid is separated from the gas. The separated liquid from the separator ( 22 ) is returned directly to the bed in the reactor ( 9 ) introduced. A pump ( 23 ) is suitably placed behind the separator ( 22 ) arranged.
  • The gas leaving the separator is sent to the bottom of the reactor ( 9 ) returned. 2 Fig. 12 illustrates another arrangement for carrying out the process of the present invention wherein the gas exiting the separator is recycled together with the gaseous stream (B).
  • 2 illustrates another arrangement for carrying out the method of the present invention, wherein the compressor ( 15 ) after the separation of the gaseous recirculation flow through the separator ( 22 ) is arranged. This has the advantage that the compressor contains a reduced amount of gas which must be compressed and therefore smaller, thereby achieving better process optimization and costs.
  • 3 illustrates another embodiment for carrying out the method of the present invention. In this arrangement, both the return lines (A) and (B) with a gas / liquid separator ( 22 . 24 ) fitted.
  • The Method according to the present invention Invention will now be further illustrated by the following examples.
  • example 1
  • 300 kg of anhydrous polyethylene powder were used as a seedbed into a fluidized bed reactor introduced with a diameter of 74 cm under nitrogen. One gaseous Mixture, heated at 90 ° C, was then introduced to the reactor. The rate of climb was 38 cm / s.
  • The components of the gaseous mixture and their respective partial pressure were: Hydrogen: 0.35 MPa ethylene: 0.5 MPa pentane: 0.35 MPa Nitrogen: 0.8 MPa
  • A schematic representation of the apparatus / process used in the present example is given in FIG 2 shown.
  • The Valve located in line A was regulated so that the gas rate 400 kg / h (line A), which is about 3.1% of the total gas recirculation rate represents. The dew point of the gaseous Mixture was 66 ° C.
  • The temperature at the outlet of the exchanger attached to the return line A was reduced to reach 65 ° C. The condensation took place in the exchanger; the condensed liquid, ie pentane, was formed from the gaseous phase (as in 2 shown in the separator 22 ) and directly introduced into the fluidized bed through a gas / liquid nozzle positioned at 0.6 m above the fluidizing grid. The liquid flow rate (pentane) was 101 per m 3 of fluidized bed per hour.
  • simultaneously was the temperature of the exchanger attached to the return line (B) was, increased accordingly, to maintain the temperature in the reactor at about 90 ° C. In fact, the exchanger must B the usual thermal loss in the return line, as well as the cooling, by the liquid evaporation in the reactor caused to compensate.
  • The Inject the condensed liquid was during held about 30 minutes before the injection of the catalyst.
  • Then became a conventional one Ziegler-Natta catalyst in the reactor at a rate of 20 g / h introduced together with a triethylaluminum cocatalyst.
  • The Production rose progressively until a constant production of 100 kg / h polyethylene was reached.
  • The outlet of the heat exchanger, which was arranged in line A and the gaseous rate flowing through it were further regulated to a condensed liquid flow rate of pentane of about 101 per m 3 of fluidized bed to obtain per hour.
  • The Polymerization took place under stable conditions. There was no pollution observed the reactor.
  • Comparative Example 2
  • The The procedure performed in this example was that described in Example 1 was carried out similarly, except that this entire recycle gas flowed through line A and therefore, the sub-line B was not used.
  • Around the temperature in the reactor before the start of the polymerization at 90 ° C to keep the temperature of the exchanger, which was in the line A was arranged, increased accordingly. Therefore, found in the exchanger no condensation taking place.
  • Of the Catalyst was injected by the same method as in Example 1, except that no condensed liquid in the return line while was present at the beginning of the catalyst injection process.
  • To approximately two hours of manufacture, polymer crusts were in production found. It was just as damaging Reactor contamination observed.
  • Comparative Example 3 - Process Event Simulation
  • A stable gas phase polymerization process was carried out in a 74 cm diameter reactor under the following conditions.
    the reactor contained 800 kg of an active polyethylene powder
    the components of the gaseous mixture and their partial pressure were: ethylene: 0.3 MPa Hydrogen: 0.21 MPa pentane: 0.33 MPa Nitrogen: 0.76 MPa
  • Of the Dew point of the gaseous Mixture was 66 ° C.
  • The Gas riser speed was 38 cm / s.
  • One conventional Ziegler-Natta was added to the reactor as a prepolymer at a rate of 1 kg / h introduced; Triethylaluminum cocatalyst in pentane also became continuous introduced at a rate of 600 ml / h.
  • The Polyethylene production was 200 kg / h.
  • The Polymerization temperature was 90 ° C.
  • The entire recycle gas flowed through Line A; Line B was not used.
  • Under these conditions, and to maintain the polymerization temperature at 90 ° C, the temperature of the exchanger (line A) was sufficient at about Cooled to 62 ° C (i.e. h., Lower than the dew point of the gaseous mixture).
  • The condensed liquid (pentane) was separated from the recycle gas into a separator and reintroduced into the reactor through a gas / liquid nozzle positioned 60 cm above the fluidization grid. The liquid injection rate was 10001 per m 3 of fluidized bed per hour.
  • Around To simulate a mechanical failure became the catalyst / prepolymer injection stopped.
  • The Manufacturing progressively decreased. Accordingly, the cooling requirement decreased of the exchanger (line A) until the temperature of the exchanger over the Dew point of the gaseous Mixture was enough, so that no more condensed liquid was generated.
  • In reached this stage (no injection of condensed liquid into the bed) the polyethylene production about 100 kg / h.
  • Approximately 40 minutes after the injection of the condensed liquid was stopped, hot spots were detected by wall thermocouples.
  • The Polymerization was stopped. When opening the reactor was the Melting of a part of the bed observed. It looked like one great Agglomerate.
  • Example 4 - Process Event Simulation
  • The Process conditions were exactly the same as those in Comparative Example 3 were used.
  • To the event simulation has been reduced manufacturing and the Inject the condensed liquid (Pentane) was also reduced, as in Comparative Example Third
  • When the flow rate of the condensed liquid reached about 401 per m 3 of fluidized bed per hour (corresponding to a PE production of 136 kg / h), a portion of the recycle gas passed through the exchanger mounted in line B, wherein the temperature was at about 72 ° C (ie, about 5 ° C above the dew point of the gaseous mixture).
  • Under these conditions it was possible the temperature at the outlet of Exchanger, which was installed in line A, to keep at about 65 ° C, this means, below the dew point of the gaseous Mixture.
  • The respective flow rates passing through lines A and B were regulated to reach about 14.4% of the total flow rate through line A, with a condensed liquid rate of about 401 per m 3 Fluid bed was held every hour.
  • The Temperature in the reactor was maintained at 90 ° C. The polyethylene production progressively decreased, and the temperature of the exchanger, the was mounted in line B, increased the corresponding.
  • No hot spots were registered during the entire procedure and subsequently were observed no agglomerates, so that high productivity rates could be achieved without any problems.

Claims (9)

  1. Continuous fluidized bed process for the polymerization of an olefin monomer selected from (a) ethylene, (b) propylene, (c) mixtures of ethylene and propylene and (d) one or more other alpha-olefins which are (a), ( b) or (c) are mixed in a fluidized bed reactor by continuously recycling a gaseous stream comprising at least one of ethylene and / or propylene through the fluidized bed in the reactor in the presence of a polymerization catalyst under reactive conditions, characterized in that recycled gaseous stream which is withdrawn from the reactor, into two streams (A and B) is divided and that (a) a first stream (A), which has been condensed to a temperature at which liquid condensed, then directly again is introduced into the fluidized bed in the reactor so that the condensed liquid at all times continuously into the bed at a minimum rate of 101 liquid per Cubic meter of fluidized bed material per hour, and (b) a second stream (B) bypassing the above cooling / condensation step is passed through a heat exchanger and then reintroduced into the reactor.
  2. The method of claim 1, wherein the condensed liquid directly into the fluidized bed above the upper limit of the temperature gradient between the incoming Fluidizing gas and the rest of the bed is introduced.
  3. Method according to one of the preceding claims, wherein the second stream (B) through the heat exchanger sufficiently heated will, to the growing cooling, from the injection of liquid results in balancing, whereby the heat balance in the process is maintained.
  4. Method according to one of claims 1 to 2, wherein the second Stream (B) through the heat exchanger a temperature cooled will, at the liquid condensed, wherein the condensed liquid prior to its introduction into the bed is disconnected from the stream.
  5. A method according to any one of claims 1 to 3, wherein the condensed liquid before their introduction in the bed from the gaseous Electricity is separated.
  6. Starting process of a continuous gas fluidized bed process for the polymerization of an olefin monomer selected from (a) ethylene, (b) propylene, (c) mixtures of ethylene and propylene and (d) one or more other alpha-olefins mixed with (a), (b) or (c), in a fluidized bed reactor by continuous recycling of a gaseous Stream comprising at least one of ethylene and / or propylene, by the fluidized bed in the reactor in the presence of a polymerization catalyst under reactive conditions, characterized in that the recycled gaseous stream, which is withdrawn from the reactor, is divided into two streams (A and B) and that (A) a first stream (A) that is at a temperature at which liquid condensed out, cooled is then reintroduced directly into the fluidized bed in the reactor so that the condensed liquid at any time continuously in the bed at a minimum Speed of 101 liquid per cubic meter of fluid bed material introduced per hour will, and (b) a second stream (B) that performs the above cooling / condensation step bypasses, is passed through a heat exchanger and then reintroduced into the reactor.
  7. The method of claim 6, wherein the second stream (B) through the heat exchanger sufficiently heated will, to the growing cooling, from the injection of liquid results in balancing, whereby the heat balance in the process is maintained.
  8. Method according to one of claims 6 or 7, wherein the polymerization catalyst is introduced directly into the fluidized bed with the stream of condensed liquid.
  9. Method according to one of claims 6 or 7, wherein the introduction of the condensed liquid in the rectal bed before the introduction of the active catalyst in the reactor begins and / or before the Polymerization takes place.
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